Citation:

GRANGE, A. H., M. C. ZUMWALT, AND G. SOVOCOOL. DETERMINATION OF ION AND NEUTRAL LOSS COMPOSITIONS AND DECONVOLUTION OF PRODUCT ION MASS SPECTRA USING AN ORTHOGONAL ACCELERATION, TIME-OF-FLIGHT MASS SPECTROMETER AND AN ION CORRELATION PROGRAM. RAPID COMMUNICATIONS IN MASS SPECTROMETRY. John Wiley & Sons, Ltd., Indianapolis, IN, 20(2):89-102, (2006).

Impact/Purpose:

Provide state-of-the-science sampling, analysis, separation, and detection methods to allow rapid, accurate field and laboratory analyses of contaminated soils, sediments, biota, and groundwater to support Superfund clean-up decisions. Apply state-of-the-science methods in chemical analysis and data interpretation (e.g., mass spectral interpretation) to actual problems of OSWER, the Regions, and the States, in cooperation with the Las Vegas Technical Support Center as well as by direct contacts with Regional and State employees. Provide technical advice and guidance to OSWER using the environmental chemistry expertise (e.g., mass spectrometry, analytical methods development, clean-up methodology, inorganics, organometallics, volatile organics, non-volatile organics, semi-volatile organics, separation technologies, etc.) found within the branch.

Technical research support for various projects initiated either by Regions/Program Offices or ECB scientists. While these efforts will support the Regions and Program Offices, they cannot be predicted or planned in advance, and may serve multiple duty (e.g., solve real-world problems, serve to ground-truth analytical approaches that ECB is developing, transfer new technology). Many of the activities in this task support requests involving enforcement decisions and therefore are categorized as "environmental forensics".

Description:

Exact masses of monoisotopic ions and the relative isotopic abundances (RIAs) of ions greater in mass by 1 and 2 Da than the monoisotopic ion are independent and complementary physical properties useful for istinguishing among ion compositions possible for a given nominal mass. Using these properties to determine compositions of product ions and neutral losses increases the mass of precursor ions for which unique compositions can be determined. Precursor ion, product ion, and neutral loss compositions aid mass spectral interpretation and guide modest chemical literature searches for candidate standards to be obtained for confirmation of tentative compound identifications. This approach is essential for compound characterization or identification due to the absence of commercial libraries of ESI and APCI product ion spectra. For a series of 34 exact mass measurements, an orthogonal acceleration time-of-flight mass spectrometer provided 34 and 29 values accurate to within 2 and 1 mDa, respectively, for ions from eight simulated unknowns with [M+H] ion masses between 166 and 319 Da. Of 36 RIA + measurements for +1 Da or +2 Da ions, 35 were accurate to within 20% of their predicted values (or to within 0.4 RIA % when the RIA value was less than 1%) in the absence of obvious interferences, when the onoisotopic ion peak areas were at least 1.7 x 10 counts, and the ion 5 masses exceeded 141 Da. An Ion Correlation Program (ICP) provided the unique and correct compositions for all but three of the 34 ions studied. Manual inspection of the data eliminated the incorrect compositions. To test the utility of the ICP for deconvoluting composite product ion spectra, all 34 ions were tested for correlation. Six of eight precursor ions were identified as such, while two were compositional subsets of others and were not properly identified. The six precursor ion compositions were still found by the ICP even though ions with masses less than 158 Da were not considered since they could no longer be correlated with a single precursor ion. Finally, two unidentified analytes were characterized, based on data published by others and using the ICP together with mass spectral interpretation.

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